CN115850807B - Degradable nano preservative film with photodynamic bactericidal activity and preparation method thereof - Google Patents
Degradable nano preservative film with photodynamic bactericidal activity and preparation method thereof Download PDFInfo
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- CN115850807B CN115850807B CN202211672047.3A CN202211672047A CN115850807B CN 115850807 B CN115850807 B CN 115850807B CN 202211672047 A CN202211672047 A CN 202211672047A CN 115850807 B CN115850807 B CN 115850807B
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- 239000003755 preservative agent Substances 0.000 title claims abstract description 56
- 230000002335 preservative effect Effects 0.000 title claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000002105 nanoparticle Substances 0.000 claims abstract description 40
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940093265 berberine Drugs 0.000 claims abstract description 33
- QISXPYZVZJBNDM-UHFFFAOYSA-N berberine Natural products COc1ccc2C=C3N(Cc2c1OC)C=Cc4cc5OCOc5cc34 QISXPYZVZJBNDM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000661 sodium alginate Substances 0.000 claims abstract description 14
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 14
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 14
- 239000004373 Pullulan Substances 0.000 claims abstract description 13
- 229920001218 Pullulan Polymers 0.000 claims abstract description 13
- 235000019423 pullulan Nutrition 0.000 claims abstract description 13
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 11
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 11
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000014103 egg white Nutrition 0.000 claims abstract description 10
- 210000000969 egg white Anatomy 0.000 claims abstract description 10
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 141
- 239000000243 solution Substances 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 239000003549 soybean oil Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000001954 sterilising effect Effects 0.000 abstract description 6
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 6
- 239000003642 reactive oxygen metabolite Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 230000000845 anti-microbial effect Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- 229920001661 Chitosan Polymers 0.000 description 4
- 241000234295 Musa Species 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 235000021015 bananas Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 241000220223 Fragaria Species 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 241000123650 Botrytis cinerea Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000419 plant extract Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000021012 strawberries Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000223602 Alternaria alternata Species 0.000 description 1
- 241001529387 Colletotrichum gloeosporioides Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
Abstract
The invention provides a degradable nano preservative film with photodynamic bactericidal activity and a preparation method thereof, belonging to the technical field of antibacterial preservative films. The invention synthesizes the berberine and citric acid which are natural plant antibacterial components into nano particles with aggregation-induced emission characteristics through self-assembly. Under white light, the nanoparticle can generate a large amount of Reactive Oxygen Species (ROS), thereby exhibiting high and durable antimicrobial activity. The nano-particles are used as a filler to be added into a membrane mixed solution consisting of sodium alginate, pullulan and egg white. The invention breaks through the bottleneck of short duration of the current antibacterial preservative film by utilizing photodynamic sterilization and can realize direct contact sterilization only by using the antibacterial agent traditionally. Meanwhile, the problem that the transparency and mechanical properties of the film are affected by adding excessive antibacterial components into the film matrix is effectively solved.
Description
Technical Field
The invention relates to the technical field of antibacterial preservative films, in particular to a degradable nano preservative film with photodynamic bactericidal activity and a preparation method thereof.
Background
Microbial contamination is a major factor causing deterioration of foods, and not only causes great economic loss but also seriously threatens human health. The incorporation of antimicrobial agents into film matrices is considered a promising approach to reduce food decay during shipping or storage. Natural extracts and metal oxide nanoparticles are the primary antibacterial substances added to active packages. Among them, ag nanoparticles, cuO nanoparticles, and ZnO nanoparticles have been demonstrated to have excellent antibacterial effects, but these metal oxide nanoparticles have poor compatibility with a film matrix, and may also cause problems of human health and environmental pollution. In contrast, natural plant extracts are considered to be ideal sources of antibacterial compounds because they are environmentally friendly, relatively safe and renewable to humans. Unfortunately, plant extracts have low antimicrobial activity and require large amounts of extracts to exhibit excellent antimicrobial activity.
Currently, aiming at the market demand of degradable antibacterial preservative films, the photosensitive antibacterial preservative film based on nano bacterial cellulose is prepared in Chinese patent CN113927965A by using nano bacterial cellulose, carboxymethyl chitosan, photosensitizer and citric acid. The antibacterial activity of carboxymethyl chitosan and citric acid is combined with the photosensitizer, so that the problem of low antibacterial activity of the preservative film is solved in a targeted manner, but the transparency and mechanical properties of the film are affected by adding various antibacterial components into the film matrix, so that the product quality is difficult to meet the market demand. Furthermore, the direct addition of a photosensitizer to the membrane matrix affects its physicochemical stability and bioavailability. In Chinese patent CN114854100A, a nano antibacterial preservative film is prepared from carboxymethyl chitosan, hydroxypropyl methylcellulose, nano titanium dioxide modified oyster shells, graded nano zinc oxide powder, nano silicon dioxide, glycerol, gallic acid, sodium alginate, polyvinyl alcohol and other materials. The method improves the antibacterial activity of the film by combining a plurality of antibacterial components, but the preparation process is complicated, and the transparency and mechanical properties of the film can be affected by adding a plurality of fillers into the film matrix. Chinese patent CN111234365A prepares a nanofiber antibacterial preservative film through EVOH nanofiber, PET nanofiber, plant essential oil composition, quaternary ammonium salt chitosan and glycerol. Although the film has good oxygen barrier property, the antibacterial persistence and the transparency of the film are poor and the preparation process is complicated.
In summary, a high-efficiency simple preparation method capable of improving the antibacterial durability of the preservative film without affecting the transparency and mechanical properties of the film is urgently needed at present.
Disclosure of Invention
The invention aims to provide a degradable nano preservative film with photodynamic bactericidal activity and a preparation method thereof, which are used for solving the technical problem that the transparency and mechanical properties of the film are affected when the antibacterial durability of the conventional preservative film is improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a degradable nano preservative film with photodynamic bactericidal activity, which is prepared from the following raw materials in parts by weight:
the nanoparticle is obtained by self-assembly of berberine and citric acid.
Further, the preparation method of the nanoparticle comprises the following steps:
1) Sodium hydroxide is used for respectively adjusting the pH value of the methanol solution of berberine and the pH value of the methanol solution of citric acid to 7.0-8.0;
2) Mixing the methanol solution of berberine obtained in the step 1) with the methanol solution of citric acid, adding into water, and stirring to obtain the nanoparticle.
Further, the concentration of the methanol solution of the berberine is 2-3wt% and the concentration of the methanol solution of the citric acid is 1-2wt%.
Further, in the step 2), the volume ratio of the methanol solution of berberine, the methanol solution of citric acid and water is 1-3: 1 to 3:50 to 60.
Further, in the step 2), the temperature of the water is 50-60 ℃, and the stirring time is 6-8 hours.
The invention provides a preparation method of a degradable nano preservative film with photodynamic bactericidal activity, which comprises the following steps:
a. mixing pullulan and sodium alginate in water, and heating until the pullulan and the sodium alginate are dissolved to obtain a mixed solution;
b. mixing the epoxidized soybean oil into the mixed solution, and then adding egg white for crosslinking reaction to obtain a crosslinked product;
c. and mixing the crosslinked product with the nano particles to obtain the degradable nano preservative film with photodynamic bactericidal activity.
Further, in the step a, the heating temperature is 100 to 110 ℃.
In the step b, the temperature of the epoxidized soybean oil mixed in the mixed solution is 80-90 ℃ and the mixing time is 30-50 min.
In the step b, the temperature of the crosslinking reaction is 30-40 ℃, and the time of the crosslinking reaction is 1-5 min.
The invention has the beneficial effects that:
the invention prepares the natural nano-particles with aggregation-induced emission characteristics by self-assembling berberine and citric acid, and the nano-particles can generate a large amount of Reactive Oxygen Species (ROS) under white light, so that the antibacterial activity of the nano-particles can be obviously enhanced. Meanwhile, the nano particles improve the physicochemical stability and bioavailability of the berberine and the citric acid in the preservative film.
The strategy of applying the plant source nano particles with aggregation-induced emission characteristic and photodynamic bactericidal activity to the degradable preservative film breaks through the limitation that only the antibacterial agent can realize direct contact sterilization in the prior art, and the visible light is utilized to improve the antibacterial performance of the film, which is a break of the antibacterial package.
The berberine, the citric acid and the egg white protein have crosslinking effect, so that the film forming property of the film mixed solution can be obviously improved, and the ductility of the film can be increased. The plant source nano particles prepared by the invention have the characteristics of safety, no toxicity and degradability. The invention provides a simple and efficient preparation process of the green synthetic photodynamic sterilization preservative film without adding any toxic substances.
Drawings
FIG. 1 is a transmission electron microscope image of the nanoparticle obtained in example 1 of the present invention;
FIG. 2 is an external view of the cling film prepared in comparative example 1 (A) and example 3 (B);
FIG. 3 is a graph showing the comparison of the antibacterial activity of the degradable nano preservative film with photodynamic bactericidal activity prepared in example 3 of the present invention;
FIG. 4 is a graph showing the effect of the degradable nano preservative film with photodynamic bactericidal activity prepared in example 3 on strawberry preservation;
fig. 5 is a graph showing the comparison of the preservation effect of the degradable nano preservative film with photodynamic bactericidal activity prepared in the embodiment 3 of the invention on bananas.
Detailed Description
The invention provides a degradable nano preservative film with photodynamic bactericidal activity, which is prepared from the following raw materials in parts by weight:
the nanoparticle is obtained by self-assembly of berberine and citric acid.
In the present invention, the pullulan is added in an amount of 50 to 60 parts by mass, preferably 52 to 58 parts by mass, and more preferably 55 parts by mass.
In the present invention, the sodium alginate is added in an amount of 30 to 40 parts by mass, preferably 32 to 38 parts by mass, and more preferably 35 parts by mass.
In the present invention, the amount of the egg white added is 5 to 10 parts by mass, preferably 6 to 9 parts by mass, and more preferably 7 to 8 parts by mass.
In the present invention, the epoxidized soybean oil is added in an amount of 0.5 to 1.0 parts by mass, preferably 0.6 to 0.9 parts by mass, and more preferably 0.7 to 0.8 parts by mass.
In the present invention, the amount of the nanoparticles added is 0.4 to 0.8 part by mass, preferably 0.5 to 0.7 part by mass, and more preferably 0.6 part by mass.
In the present invention, the method for preparing the nanoparticle comprises the steps of:
1) Sodium hydroxide is used for respectively adjusting the pH value of the methanol solution of berberine and the pH value of the methanol solution of citric acid to 7.0-8.0;
2) Mixing the methanol solution of berberine obtained in the step 1) with the methanol solution of citric acid, adding into water, and stirring to obtain the nanoparticle.
In the present invention, the pH of the methanol solution of berberine and the methanol solution of citric acid is preferably adjusted to 7.5.
In the present invention, the concentration of the methanol solution of berberine is 2 to 3wt%, preferably 2.2 to 2.8wt%, and more preferably 2.5wt%; the concentration of the methanol solution of citric acid is 1 to 2wt%, preferably 1.2 to 1.8wt%, and more preferably 1.5wt%.
In the invention, in the step 2), the volume ratio of the methanol solution of berberine, the methanol solution of citric acid and water is 1-3: 1 to 3:50 to 60, preferably 1.5 to 2.5:1.5 to 2.5:52 to 58, more preferably 2:2:55.
in the present invention, in the step 2), the temperature of the water is 50 to 60 ℃, preferably 52 to 58 ℃, and more preferably 55 ℃; the stirring time is 6 to 8 hours, preferably 7 hours.
The invention provides a preparation method of a degradable nano preservative film with photodynamic bactericidal activity, which comprises the following steps:
a. mixing pullulan and sodium alginate in water, and heating until the pullulan and the sodium alginate are dissolved to obtain a mixed solution;
b. mixing the epoxidized soybean oil into the mixed solution, and then adding egg white for crosslinking reaction to obtain a crosslinked product;
c. and mixing the crosslinked product with the nano particles to obtain the degradable nano preservative film with photodynamic bactericidal activity.
In the present invention, the heating temperature in the step a is 100 to 110 ℃, preferably 102 to 108 ℃, and more preferably 105 ℃.
In the present invention, in the step b, the temperature of mixing the epoxidized soybean oil in the mixed solution is 80 to 90 ℃, preferably 82 to 88 ℃, and more preferably 85 ℃; the mixing time is 30 to 50 minutes, preferably 35 to 45 minutes, and more preferably 40 minutes.
In the present invention, in the step b, the temperature of the crosslinking reaction is 30 to 40 ℃, preferably 32 to 38 ℃, and more preferably 35 ℃; the crosslinking reaction time is 1 to 5 minutes, preferably 2 to 4 minutes, and more preferably 3 minutes.
In the invention, berberine (purity is more than or equal to 98 percent, solid particles) is provided by Shanghai Aba Ding Shenghua technology Co., ltd; citric acid (purity >99.5%, solid particles) was supplied by Shanghai Meilin Biotechnology Co.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) The berberine and the citric acid are weighed and respectively added into the methanol solution to obtain a methanol solution of 2 weight percent of berberine and a methanol solution of 1 weight percent of citric acid. The methanol solution of berberine and the methanol solution of citric acid were adjusted to ph=7.0 with sodium hydroxide, respectively.
(2) Mixing and stirring the methanol solution of berberine and the methanol solution of citric acid in the step (1) at the temperature of 20 ℃ according to the proportion of 1:1 (v/v), and then adding 3mL of the mixed solution into 50mL of distilled water, wherein the temperature of the distilled water is kept at 50 ℃, and stirring strongly for 6 hours to obtain the nano particles.
(3) 50 parts of pullulan and 30 parts of sodium alginate are weighed and added into 200 parts of distilled water, and the mixture is heated in a boiling water bath at 100 ℃ until the solute is completely dissolved, so as to obtain a mixed solution.
(4) Mixing the mixed solution with 0.5 part of epoxidized soybean oil, stirring at a constant temperature of 80 ℃ for 30min, cooling to 30 ℃, and adding 5 parts of egg white for reaction for 5min.
(5) Mixing the crosslinked product with 0.4 part of nano particles, stirring for 20min at 20 ℃ to obtain a degradable nano preservative film solution with photodynamic bactericidal activity, and carrying out tape casting film forming on an acrylic flat plate, and drying for later use.
Example 2
(1) The berberine and the citric acid are weighed and respectively added into the methanol solution to obtain a methanol solution of 2.5 weight percent of berberine and a methanol solution of 1.5 weight percent of citric acid. The methanol solution of berberine and the methanol solution of citric acid were adjusted to ph=7.5 with sodium hydroxide, respectively.
(2) Mixing and stirring the methanol solution of berberine and the methanol solution of citric acid in the step (1) at the temperature of 24 ℃ according to the proportion of 1:1.5 (v/v), and then adding 4mL of the mixed solution into 55mL of distilled water, wherein the temperature of the distilled water is kept at 55 ℃, and stirring strongly for 7h to obtain the nano particles.
(3) 55 parts of pullulan and 35 parts of sodium alginate are weighed and added into 200 parts of distilled water, and the mixture is heated in a boiling water bath at 100 ℃ until the solute is completely dissolved, so as to obtain a mixed solution.
(4) Mixing the mixed solution with 0.8 part of epoxidized soybean oil, stirring at a constant temperature of 90 ℃ for 40min, cooling to 35 ℃, and adding 8 parts of egg white for reaction for 5min.
(5) Mixing the crosslinked product with 0.6 part of nano particles, stirring for 25min at 25 ℃ to obtain a degradable nano preservative film solution with photodynamic bactericidal activity, and carrying out tape casting film forming on an acrylic flat plate, and drying for later use.
Example 3
(1) The berberine and the citric acid are weighed and respectively added into the methanol solution to obtain a methanol solution of 3 weight percent of berberine and a methanol solution of 2 weight percent of citric acid. The methanol solution of berberine and the methanol solution of citric acid were adjusted to ph=8.0 with sodium hydroxide, respectively.
(2) Mixing and stirring the methanol solution of berberine and the methanol solution of citric acid in the step (1) at the temperature of 28 ℃ according to the ratio of 1:2 (v/v), and then adding 5mL of the mixed solution into 60mL of distilled water, wherein the temperature of the distilled water is kept at 60 ℃, and stirring strongly for 8 hours to obtain the nano particles.
(3) 60 parts of pullulan and 40 parts of sodium alginate are weighed and added into 200 parts of distilled water, and the mixture is heated in a boiling water bath at 100 ℃ until the solute is completely dissolved, so as to obtain a mixed solution.
(4) Mixing the mixed solution with 1.0 part of epoxidized soybean oil, stirring at a constant temperature of 90 ℃ for 50min, cooling to 40 ℃, and adding 10 parts of egg white for reaction for 5min.
(5) Mixing the crosslinked product with 0.8 part of nano particles, stirring for 30min at 30 ℃ to obtain a degradable nano preservative film solution with photodynamic bactericidal activity, and carrying out tape casting film forming on an acrylic flat plate, and drying for later use.
Comparative example 1
(1) 60 parts of pullulan and 40 parts of sodium alginate are weighed and added into 200 parts of distilled water, and the mixture is heated in a boiling water bath at 100 ℃ until the solute is completely dissolved, so as to obtain a mixed solution.
(2) Mixing the mixed solution with 1.0 part of epoxidized soybean oil, stirring at a constant temperature of 90 ℃ for 50min, cooling to 40 ℃, and adding 10 parts of egg white for reaction for 5min.
(3) Stirring the crosslinked product at 30 ℃ for 30min to obtain a preservative film solution, casting the preservative film solution on an acrylic flat plate to form a film, and drying for later use.
The nanoparticle solution obtained in example 1 was dried on a conductive resin in vacuum at room temperature and then photographed by a TEM, and it can be seen from fig. 1 that the prepared nanoparticles were mostly approximately uniform spherical particles with a size of about 40 to 50nm.
Fig. 2 a shows the preservative film of comparative example 1 without nanoparticles, and fig. B shows the nano preservative film prepared in example 3 of the present invention, and it can be seen from fig. 2 that the added nanoparticles have no influence on the transparency of the preservative film.
FIG. 3 shows the preservative film prepared in example 3 cut into a round with a diameter of 0.6cm, and then placed in the center of a Petri dish filled with Botrytis cinerea and Alternaria alternata, respectively. The dishes were incubated at 28℃in white light and dark environment, respectively, for 72h, and the antibacterial effect of the films was observed. From fig. 3, it can be clearly seen that the nano preservative film has a good inhibition effect on botrytis cinerea and colletotrichum gloeosporioides under white light.
Fig. 4 is a comparison of the nano preservative film (A2) prepared in example 3 with a commercially available PE preservative film (A1). As is evident from fig. 4, the strawberries packed with PE preservative film at 20 ℃ already show a significant decay at 6d, while the strawberries packed with nano preservative film still do not show any decay at 6 d.
Fig. 5 is a comparison of the nano preservative film (A2) prepared in example 3 with a commercially available PE preservative film (A1). The nano preservative film of the embodiment 3 is used for prolonging the shelf life of bananas, can obviously inhibit the browning rate of bananas, and has a good protective effect on the storage quality of bananas.
From the above embodiments, the present invention provides a degradable nano preservative film with photodynamic bactericidal activity and a preparation method thereof. The invention breaks through the bottleneck of short duration of the current antibacterial preservative film by utilizing photodynamic sterilization and can realize direct contact sterilization only by using the antibacterial agent traditionally. Meanwhile, the problem that the transparency and mechanical properties of the film are affected by adding excessive antibacterial components into the film matrix is effectively solved. In addition, the self-assembly preparation of the nano-particles solves the problem that the physical and chemical stability and the bioavailability of the plant active ingredients or the photosensitizer are affected by directly adding the plant active ingredients or the photosensitizer into the membrane matrix. The degradable nano preservative film with photodynamic bactericidal activity prepared by the invention not only has high-efficiency durable antibacterial activity, but also has good transparency and mechanical property, simple and convenient preparation process, and is green and pollution-free. Compared with the PE preservative film sold in the market, the preservative film can effectively prolong the shelf life of fresh fruits and vegetables by more than 2-3 d. The nano preservative film has very wide application prospect in the field of fruit and vegetable preservation.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The degradable nano preservative film with photodynamic bactericidal activity is characterized by being prepared from the following raw materials in parts by weight:
50-60 parts of pullulan;
30-40 parts of sodium alginate;
5-10 parts of egg white;
0.5 to 1.0 part of epoxidized soybean oil;
0.4 to 0.8 portion of nano particles;
the nano particles are obtained by self-assembly of berberine and citric acid;
the preparation method of the nanoparticle comprises the following steps:
1) Sodium hydroxide is used for respectively adjusting the pH value of the methanol solution of berberine and the pH value of the methanol solution of citric acid to 7.0-8.0;
2) Mixing the methanol solution of berberine obtained in the step 1) with the methanol solution of citric acid, adding into water, and stirring to obtain the nanoparticle.
2. The degradable nano preservative film with photodynamic bactericidal activity according to claim 1, wherein the concentration of the methanol solution of berberine is 2-3wt% and the concentration of the methanol solution of citric acid is 1-2wt%.
3. The degradable nano preservative film with photodynamic bactericidal activity according to claim 1 or 2, wherein in the step 2), the volume ratio of the methanol solution of berberine, the methanol solution of citric acid and water is 1-3:1-3:50-60.
4. The degradable nano preservative film with photodynamic bactericidal activity according to claim 3, wherein in the step 2), the temperature of water is 50-60 ℃, and the stirring time is 6-8 hours.
5. The method for preparing the degradable nano preservative film with photodynamic bactericidal activity as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
a. mixing pullulan and sodium alginate in water, and heating until the pullulan and the sodium alginate are dissolved to obtain a mixed solution;
b. mixing the epoxidized soybean oil into the mixed solution, and then adding egg white for crosslinking reaction to obtain a crosslinked product;
c. and mixing the crosslinked product with the nano particles to obtain the degradable nano preservative film with photodynamic bactericidal activity.
6. The method according to claim 5, wherein in the step a, the heating temperature is 100 to 110 ℃.
7. The method according to claim 5 or 6, wherein in the step b, the epoxidized soybean oil is mixed in the mixed solution at a temperature of 80 to 90 ℃ for a time of 30 to 50 minutes.
8. The method according to claim 7, wherein in the step b, the temperature of the crosslinking reaction is 30 to 40℃and the time of the crosslinking reaction is 1 to 5 minutes.
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| CN112494463A (en) * | 2020-11-23 | 2021-03-16 | 潍坊医学院 | Berberine/mineralized collagen composite membrane and preparation method and application thereof |
| CN113927965A (en) * | 2021-12-07 | 2022-01-14 | 江南大学 | Photosensitive antibacterial antioxidant composite preservative film based on nano bacterial cellulose and preparation method and application thereof |
| CN114854100A (en) * | 2022-06-01 | 2022-08-05 | 安徽天添塑业有限公司 | Nano antibacterial preservative film and preparation process thereof |
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| CN112010849A (en) * | 2019-05-29 | 2020-12-01 | 北京中医药大学 | Flavonoid glycoside and isoquinoline alkaloid complex for inhibiting multiple drug-resistant staphylococcus aureus and preparation of carrier-free nano-drug thereof |
| CN110755610A (en) * | 2019-09-29 | 2020-02-07 | 天津科技大学 | Antibacterial hydrogel with aggregation-induced emission characteristic and preparation method thereof |
| CN112494463A (en) * | 2020-11-23 | 2021-03-16 | 潍坊医学院 | Berberine/mineralized collagen composite membrane and preparation method and application thereof |
| CN113927965A (en) * | 2021-12-07 | 2022-01-14 | 江南大学 | Photosensitive antibacterial antioxidant composite preservative film based on nano bacterial cellulose and preparation method and application thereof |
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